DE1768096B2 - PROCESS FOR THE PREPARATION OF 2-METHYL-2-PENTENE - Google Patents

PROCESS FOR THE PREPARATION OF 2-METHYL-2-PENTENE

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Publication number
DE1768096B2
DE1768096B2 DE19681768096 DE1768096A DE1768096B2 DE 1768096 B2 DE1768096 B2 DE 1768096B2 DE 19681768096 DE19681768096 DE 19681768096 DE 1768096 A DE1768096 A DE 1768096A DE 1768096 B2 DE1768096 B2 DE 1768096B2
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Prior art keywords
pentene
nickel
methyl
aluminum
solvent
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DE19681768096
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German (de)
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DE1768096A1 (en
DE1768096C3 (en
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Ernest H. Corpus Christi Tex.; Neal Arthur H. Baton Rouge La.; Drew (V.StA.)
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2291—Olefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

Die Erfindung betrifft ein Verfahren zum Herstellen von 2-Methyl-2-penten durch Dimerisation von Propylen in Gegenwart eines Ubergangsmetallacetonats und eines AlkylaluminiumhalogenidsThe invention relates to a method of manufacture of 2-methyl-2-pentene by dimerization of propylene in the presence of a transition metal acetonate and an alkyl aluminum halide

Es sind bereits verschiedene Verlahren zur katalytischen Polymerisation von Propen bekannt Die bei diesen Verfahren erhaltenen Produkte enthalten jedoch betrachtliche Mengen an Verbindungen mit höherem Molekulargewicht als das der Hexene, die Verteilung der Verbindungen im Reaktionsprodukt entspricht im allgemeinen einer Poissonschen Verteilung Auch die Dimerisation von Propen in Gegenwart von Nickel- oder Kobalt-Acetylacetonat und einem Alkylaluminiumhalogenid ist bereits bekannt, beispielsweise aus der belgischen Patentschrift 6 86 496, ferner ist gemäß der franzosischen Patentschrift 14 20 952 auch schon die selektive Dimerisierung zu 2-Methyl-2-penten möglich Die bekannten Verfahren haben jedoch den Nachteil, daß das besonders erwünschte Dimensierungsprodukt, das als Vorprodukt fur die Isoprenherstellung benotigte 2 Methyl-2-penten, in vergleichsweise nur geringen Mengen, wie beispielsweise etwa 20° ο anfalltThere are already various methods of catalytic Polymerization of propene known. However, the products obtained in these processes contain considerable amounts of compounds with higher Molecular weight than that of the hexenes, which corresponds to the distribution of the compounds in the reaction product generally a Poisson distribution Also the dimerization of propene in the presence of nickel or cobalt acetylacetonate and an alkyl aluminum halide is already known, for example from Belgian patent specification 6 86 496, furthermore is according to the French patent specification 14 20 952 also allows for selective dimerization 2-methyl-2-pentene possible However, the known processes have the disadvantage that the particularly desirable Dimensioning product that is used as a preliminary product 2 methyl-2-pentene required for isoprene production, in comparatively only small amounts, such as about 20 ° ο occurs

Der Erfindung hegt die Aufgabe zu Grunde, ein Verfahren zu schaffen, das eine äußerst selekfve Dimerisation zu 2-Methyl 2-penten ermöglicht und bei dem dieses Isomere in gegenüber bisher bekannten Verfahren erheblich größeren Mengen gebildet wer den kannThe invention is based on the object Process to create an extremely selective dimerization to 2-methyl-2-pentene enables and at which this isomer is formed in considerably larger amounts compared to previously known processes can

Diese Aufgabe wird gelost mittels eines Verfahrens der eingangs angegebenen Art zur Herstellung von 2 Methyl 2 penten durch Dimerisation von Propen in Gegenwart eines Ubergangsmetallacetonats und eines Alkylaluminiumhalogenids, das erfindungsgemaß dadurch gekennzeichnet ist, daß man in Gegenwart eines Losungsmittels bei einer Temperatur von etwa — 7 bis ^8 C in Anwesenheit eines Katalysatorkomplexes aus a) Nickelacetylacetonat, b) Diathylaluminiumcplond, Athylaluminiumdichlond oder deren Mischungen und c) 1 S-Cyclooctadien, wobei das Veihdltnis von Aluminium /u Nickel mindestens etwa 2 1 betragt, dimensiert und das Reaktionsprodukt abtrenntThis task is solved by means of a procedure of the type specified above for the production of 2 methyl 2-pentene by dimerization of propene in Presence of a transition metal acetonate and an alkyl aluminum halide according to the invention is characterized in that one in the presence of a solvent at a temperature of about - 7 to ^ 8 C in the presence of a catalyst complex from a) nickel acetylacetonate, b) dietary aluminum chloride, Ethylaluminum dichloride or their Mixtures and c) 1 S-cyclooctadiene, where the Ratio of aluminum / u nickel at least about 2 1 is dimensioned and the reaction product is separated off

Mit dem erfmdungsgemaßen Veilahren gelingt die gesteuerte Dimensiciung von Propylen in einer Stute zu einem Pioduklgemisch mit hohem Hexengehalt und insbesondeie mit hohem Gehalt an 2-Methyl-2-penten Dieses eignet sich, da es cm einzelnes Kohlenstoffatom in /«-Stellung zur Doppelbindung aufWith the method according to the invention, the succeeds controlled dimensioning of propylene in a mare to a product mixture with a high hexene content and especially high in 2-methyl-2-pentene This is suitable because it is a single carbon atom in / «- position to double bond

ίο weist, ebenso wie das 2 i-Dimeth\ 1-1 buten das beim ertindungsgemaßen Verlahren zusätzlich jedoch in vergleichsweise geringen Mengen, anfallt bevorzugt zur Herstellung von Isoprenίο shows, just like the 2 i-dimeth \ 1-1 buten, that with according to the invention, however, in addition comparatively small amounts, preferred for the production of isoprene

Es wurde testgestellt, daß beim eitindungsgemaßen Verfahren die Selektivität der Dimensalionsieaktion zur Bildung des Isomeren 2-Meth\l-2 penten zunimmt, wenn in Anwesenheit eines Katalvsators dimensiert wird dessen Verhältnis von Aluminium zu Nickel hoher als 2 I hegt Vorzugsweise wird in An-Wesenheit von solchen Katalysatoren gearbeitet, deren Verhältnis von Aluminium zu Nickel etwa 5 1 bis etwa 15 1 betragtIt has been tested that in the time according to the invention Process the selectivity of the Dimensalionsieaktion to form the isomer 2-meth \ l-2 pentene increases when dimensioned in the presence of a catalyst If the ratio of aluminum to nickel is higher than 2 I, preference is given to in-essence worked by such catalysts, the ratio of aluminum to nickel about 5 1 to is about 15 1

Die Selektivität zur Bildung des gewünschten Isomeren laßt sich auch durch die Polarität des verwendeten Losungsmittels beeinflussen Hohe Losungsmittelpolaritat begünstigt die F-rzielung hoher Aus beuten an 2-Methyl 2 penten und dementsprechend ist es vorteilhaft daß man beim erfmdungsgemaßen Verfahren in Gegenwart eines Losungsmittels dimerisiert, daß eine Dielektrizitätskonstante von mindestens 2,5 bei 20 C, vorzugsweise von etwa 5,0 bis 20, aufweistThe selectivity to form the desired isomer can also be determined by the polarity of the used Solvents affect High solvent polarity favors the achievement of high levels beutes of 2-methyl-2-pentene and accordingly it is advantageous that one in the erfmdungsgemaßen Process dimerizes in the presence of a solvent, that a dielectric constant of at least 2.5 at 20 C, preferably from about 5.0 to 20

Man kann als Einsatzmaterial Propylen odei ein propylenhaltiges Gas verwenden und die Reaktion in verschiedenen Losungsmitteln durchfuhren Geeignete Losungsmittel sind solche mit 1 bis etwa 12 Kohlenstoffatomen im Molekül, ζ B ahphatische Kohlenwasserstoffe wie Pcntan, Hexan, Heptan und/ oder aromatische Kohlenwasserstoffe wie Benzol, Toluol, Xylol oder substituierte Kohlenwasserstoffe wie Chloroform, Athylendibromid, chlorierte Xylole, Brombenzol sowie insbesondere die Dielektrizitätskonstanten von 5 0 bis 20, gemessen bei 20 C auf weisenden Losungsmittel Chlorbenzol, Dichlorbenzol und p-ChlortoluolPropylene can be used as the feedstock Use propylene-containing gas and carry out the reaction in various solvents Solvents are those with 1 to about 12 Carbon atoms in the molecule, ζ b ahphatic Hydrocarbons such as pentane, hexane, heptane and / or aromatic hydrocarbons such as benzene, Toluene, xylene or substituted hydrocarbons such as chloroform, ethylene dibromide, chlorinated xylenes, Bromobenzene and especially the dielectric constant from 5 0 to 20, measured at 20 C with solvents chlorobenzene, dichlorobenzene and p-chlorotoluene

Das Katalysatorgemisch bzw der Katalysatorkomplex enthalt zumindest anfänglich das Nickelenolat von Acetylaceton sowie eine der Alkylaluminiumhalogenid-Verbindungen Diathylaluminiumchlond oder Athylalummiumdichlorid oder deren Mischungen und zusätzlich 1,5-Cyclooctadien Dieser Olefin-Zusatz wird dem Katalysator bei der Herstellung dea Katalysatorkomplexes oder -gemisches zugesetzt und ist, soweit die Anmelderin bisher theoretisch untersuchen konnte zumindest weitgehend mit verantwoithch dafür, daß die Dimerisation von Propen äußerst selektiv zu 2-Methyl 2-penten verlauft Wahrscheinlich wird bei der Dimerisation durch diesen erfm dungsgemaß eingesetzten Katalysatorkomplex die innere vinyhsche Kohlenstoff Wasserstoff Bindung des Propens aktiviert, was zur Bildung von 2-Methyl-2-penten fuhrtThe catalyst mixture or the catalyst complex contains at least initially the nickel enolate of acetylacetone and one of the alkyl aluminum halide compounds Dietary aluminum chloride or ethyl aluminum dichloride or mixtures thereof and additionally 1,5-cyclooctadiene This olefin additive is dea the catalyst in the production Catalyst complex or mixture added and is, as far as the applicant has previously investigated theoretically could at least be largely responsible that the dimerization of propene is extreme proceeds selectively to 2-methyl-2-pentene The catalyst complex used according to the invention has the inner vinyl carbon-hydrogen bond of propene activated, which leads to the formation of 2-methyl-2-pentene

Beim erfmdungsgemaßen Verfahren wird die Reaktion bei Temperaturen im Bereich von etwa — 7 bis 38° C durchgeführt Es kann bei Atmospharendruck oder Überdruck gearbeitet werden, vorzugsweise wird ein Druck zwischen etwa Atmospharendruck und etwa 35 kg/cm2 und insbesondere zwi-In the process according to the invention, the reaction is carried out at temperatures in the range from about -7 to 38 ° C. It can be carried out at atmospheric pressure or overpressure, preferably a pressure between about atmospheric pressure and about 35 kg / cm 2 and in particular between

3 43 4

sehen etv\a Atmospharendruck und etwa 7 kg/cm2 Olefin %see etv \ a atmospheric pressure and about 7 kg / cm 2 olefin%

angewendet 4^1ethyl-l-penten 05applied 4 ^ 1ethyl-l-pentene 05

Bei einer bevorzugten Ausfuhrungsform des erfin- 2 3-Dimethyl-l-buten 1 2In a preferred embodiment of the inven- 2 3-dimethyl-1-butene 1 2

dungsgemaßen Verfahrens enthalt das Reaklionspio- 4-Methyl-2-penten 6 0according to the process contains the Reaklionspio- 4-methyl-2-pentene 6 0

dukt etwa 50 bis etwa 90 Gewichtsprozent und mehr, 5 2-Methvl-l-penten 3 7Dukt about 50 to about 90 percent by weight and more, 5 2-Methvl-1-pentene 3 7

vorzugsweise etwa 70 bis etwa 90 Gewichtsprozent τ Hexen 19 4preferably about 70 to about 90 percent by weight τ hexene 19 4

und mehr Hexene. Vorzugsweise hegen 40 bis etwa 2-Methyl-2-penten 60^0and more witches. Preferably from 40 to about 2-methyl-2-pentene 60 ^ 0

70 Gewichtsprozent der Hexene als 2-Methyl-2-pen- 2-Hexen 3 770 percent by weight of the hexenes as 2-methyl-2-pen-2-hexene 3 7

ten vor Das gewünschte Piodukt wird im allgemeinen ^ 3-Dimethvl-">-buten 5 5The desired product is generally ^ 3-Dimethvl - "> - butene 5 5

durch Destillation bei Atmospharendruck oder unter ioby distillation at atmospheric pressure or below io

Vakuum aus dem Reaktionsgemisch gewonnen. Die Katalysatorleistung, berechnet als Produktgewicht je eingesetztes Nickelgewicht, lag wesentlichVacuum gained from the reaction mixture. The catalyst performance calculated as product weight depending on the weight of nickel used, was essential

BeisP'el ' über 5000. Beis P ' el ' over 5000.

Propylen wurde unter Verwendung eines Kataly- . _Propylene was made using a catalyst. _

satorskomplexes aus Nickelacetylacetonat, Diathyl- 15 1 s ρ 1Sator complex of nickel acetylacetonate, diethyl 15 1 s ρ 1

amnioniumchlorid und 1,5-CycIooctadien mit einem Es wurde wie in Beispiel 1 beschrieben gearbeitet, AluminiumNickel-Verhaltnis von 14 I zu 87° ο mit jedoch wurde als Lösungsmittel Chlorbenzol emge-6O°/o Selektivität fur 2-Methyl-2-penten dimerisiert. setzt. Die Selektivität des Systems tür Hexene lag Hierzu wurde ein glasausgekleideter Ruhrbehälter über 90%, und die Ausbeute an 2-Mcth)l-2-penten mit Kuhler und Temperaturregistnergerat zunächst 20 war noch höher als in Beispiel 1 angegeben mit 26 Gewichtsteilen einer Losung von äquimolaren Es wurde gefunden, daß bei Erhöhung des Ver-Mengen Nickelacetylacetonat und !,S-Cyclooctadien haltnisses von Aluminium zu Nickel im Katalysatorin Toluol beschickt. Dann wurden etwa 14 Gewichts- komplex von etwa 2 1 auf etwa 5 1 die Geschwmdigteile einer Losung von äquimolaren Mengen Diathyl- keit des Propjlemerbrauchs um ein Mehrfaches analummiumchlond und Athylaluminiumdichlorid in 25 steigt. Wenn das Verhältnis von Aluminium zu Nickel Hexan unter Stickstoff bei 25C C in den Behalter ge- zwischen 5:1 und 14:1 hegt, steigt die Geschwindiggeben. Anschließend wurde bei 2,8 kg'cm2 und 29 keit langsamer an. Eine weitere Erhöhung des AIubis 33 C Propylen eingeleitet, welches mit einer Ge- minium:Nickel-Verhaltnisses über etwa 14 I hinaus schwindigkeit von 6,6 10 2 Mol/min verbraucht hat nur noch wenig Einfluß auf die Reaktionsgewurde Nach Umsetzung von 1 Mol Propylen wurde 3° schwindigkeit und auf die Olefinverteilung im Prodie folgende Verteilung von Hexenolefinen ermittelt: dukt.Amnionium chloride and 1,5-CycIooctadiene with an It was worked as described in Example 1, aluminum-nickel ratio of 14 I to 87 ° ο with, however, chlorobenzene was dimerized as a solvent of 60% selectivity for 2-methyl-2-pentene . puts. The selectivity of the system for Hexene was for this purpose, a glass-lined Ruhr tank over 90%, and the yield of 2-Mcth) l-2-pentene with a cooler and temperature register initially 20 was even higher than specified in Example 1 with 26 parts by weight of an equimolar solution It has been found that when the amount of Ver nickel acetylacetonate and!, S-Cyclooctadiene content of aluminum to nickel in the catalyst in toluene is increased. Then about 14 weight complexes increased from about 2 liters to about 5 liters. If the ratio of aluminum to nickel-hexane is between 5: 1 and 14: 1 under nitrogen at 25 C in the container, the speed increases. Subsequently, at 2.8 kg cm 2 and 29, the speed slowed down. A further increase in the AIubis 33 C propylene initiated, which with a minium: nickel ratio above about 14 I consumes a speed of 6.6 10 2 mol / min has little effect on the reaction. After conversion of 1 mol of propylene 3 ° speed and on the olefin distribution in the Prodie the following distribution of hexene olefins was determined: duct.

Claims (3)

PatentansprücheClaims 1 Verfahren zur Herstellung von 2-Methyl-2-penten duieh Dimerisation von Piopylen in Gcgenwait eines Ubergangsmetallacetonats und eines Alkylaluminiumhalogenids, dadurch ge kennzeichnet daß man in Gegenwart eines Losimgsmittels bei einer Temperatur von etwa — 7 bis 38 C in Anwesenheit eines Kata lysatorkomplexes aus a) Nickelacetylacctonat b) Diathylaluminiumchlond, Athylalummiumdichlond oder deren Mischungen und c) 1,5-CveIooctadien wobei das Verhältnis von Aluminium zu Nickel mindestens etwa 2 1 betragt, dimeiisiert und das Reaktionsprodukt abtrennt1 Process for the production of 2-methyl-2-pentene duieh dimerization of propylene in Gcgenwait a transition metal acetonate and an alkyl aluminum halide, thereby ge indicates that one is in the present a solvent at a temperature of about - 7 to 38 C in the presence of a kata lysator complex from a) nickel acetylacctonate b) Dietary aluminum chloride, ethyl aluminum dichloride or mixtures thereof and c) 1,5-CveIooctadiene the ratio of aluminum to nickel being at least about 2 1, dimeiized and separating the reaction product 2 Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man in Anwesenheit eines Katalysators dimensiert, dessen Verhältnis von AIu minium zu Nickel etwa 5 1 bis etwa 15 1 betiagt2 The method according to claim 1, characterized in that in the presence of a catalyst dimensioned whose ratio of AIu minium to nickel about 5 1 to about 15 1 3 Verfahren nach Anspruch 1 oder 2 daduich gekennzeichnet, daß man in Gegenwart eines Losungsmittels dimensiert, das eine Dielektrizitätskonstante bei 20 C von mindestens 2,5, vorzugsweise etwa 5,0 bis 20 aufweist3 method according to claim 1 or 2 daduich characterized in that one is in the presence of a solvent dimensioned that has a dielectric constant at 20 C of at least 2.5, preferably about 5.0-20
DE19681768096 1967-04-18 1968-03-30 Process for the preparation of 2-methyl-2-pentene Expired DE1768096C3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US63160767A 1967-04-18 1967-04-18
US63160767 1967-04-18

Publications (3)

Publication Number Publication Date
DE1768096A1 DE1768096A1 (en) 1971-10-07
DE1768096B2 true DE1768096B2 (en) 1976-07-08
DE1768096C3 DE1768096C3 (en) 1977-02-17

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Publication number Publication date
DE1768096A1 (en) 1971-10-07
BE713781A (en) 1968-10-17
JPS5028405B1 (en) 1975-09-16
NL157882B (en) 1978-09-15
FR1560865A (en) 1969-03-21
US3564070A (en) 1971-02-16
SE357551B (en) 1973-07-02
NL6805082A (en) 1968-10-21
GB1167289A (en) 1969-10-15

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